The hydroxylation of phenol (a substrate containing an electron donor group) and of benzoic acid (a substrate containing an electron withdrawing group) has been carried out by the photocatalytic method in aqueous suspensions containing commercial or home prepared TiO2 samples. The aim of the work was to study the distribution of hydroxylation products when different photocatalysts were used and to correlate the selectivity to some physico-chemical features of the powders. The samples were characterized by Xray diffraction, thermogravimetry, determination of crystalline phase percentage, specific surface area and zero charge point. The photoreactivity results indicate that the products of the primary oxidation of phenol are the ortho- and para-mono-hydroxy derivatives while those of benzoic acid are all the monohydroxy derivatives independently of the catalyst. The selectivity toward mono-hydroxy derivatives shows a strong dependence on catalyst hydroxylation and crystallinity degrees: the highest selectivity values were obtained by using the commercial samples that resulted the least hydroxylated and the most crystalline ones. A kinetic model, taking into account the mineralization and the partial oxidation reaction routes, is proposed by using the Langmuir-Hinshelwood model. (C) 2012 Published by Elsevier B.V.